Lithium Intercalation into the Jarosite-type Hydroxysulfate: A Topotactic Reversible Reaction from a Crystalline Phase to an Inorganic Polymer-like Structure

Gnanavel, M.; Pralong, V.; Lebedev, Oleg I.; Caignaert, V.; Bazin, P.; Raveau, B.

doi:10.1021/cm501735t

Cited by 31 publications

(50 citation statements)

References 18 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…3, in contrast to the well crystallized starting hydroxysulfate. Similar kinds of results were observed during lithium insertion into NaFe 3 (SO 4 ) 2 (OH) 6 [22]. First discharged sample of EDX and Na atomic absorption analysis confirmed that the Na:Fe:S composition corresponds to the 3:3:2 ratio.…”

Section: Contents Lists Available At Sciencedirectsupporting

confidence: 72%

“…one octahedron thick, and consequently can easily be corrugated in an aleatory way during sodium intercalation, so that they may lose their bi-dimensional periodicity, keeping their polyhedra as well as all the Fe-O-Fe and most of the Fe-O-S bonds. Finally the sodium intercalation tends to separate the layers, which can then move at random with respect to each other, exactly as described in detail in our previous report [22]. Further continuous charge/discharge cycling shows that this process involving a transition from an amorphous phase to the crystalline Jarosite structure is reversible.…”

Section: Contents Lists Available At Sciencedirectsupporting

confidence: 58%

“…Fig. 5a shows the IR spectrum of as-prepared Jarosite hydroxysulfate NaFe 3 (SO 4 ) 2 (OH) 6 , with seven main absorption peaks in the range of 400 to 4000 cm − 1 [22,23]. Observed IR bands at 481 and 514 cm − 1 were assigned to Fe-O vibrations.…”

Section: Contents Lists Available At Sciencedirectmentioning

confidence: 99%

“…In the search of a new matrix for sodium insertion, we explore the hydroxysulfate phases. Indeed, the introduction of hydroxyl groups into the sulfate matrix has opened the route to materials with promising electrode performances for Li ion batteries [20][21][22]. In the system Na-Fe-SO 4 -OH, only four phases are reported: the Natrojarosite NaFe 3 (SO 4 ) 2 (OH) 6 and the Jarosite Na 0.84 Fe 2.86 (SO 4 ) 2 (OH) 6 and two hydrated phases the Sideronatrite Na 2 FeOH(SO 4 ) 2 .3H 2 O and the Metasideronatrite Na 2 FeOH(SO 4 ) 2 ·H 2 O; these phases are minerals but could be prepared by precipitation or under hydrothermal conditions.…”

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Reversible transformation from amorphouse Na3Fe3(SO4)2(OH)6 to crystallized NaFe3(SO4)2(OH)6 Jarosite-type hydroxysulfate

et al. 2015

Self Cite

View full text Add to dashboard Cite

Section: Contents Lists Available At Sciencedirectsupporting

confidence: 72%

Section: Contents Lists Available At Sciencedirectsupporting

confidence: 58%

Section: Contents Lists Available At Sciencedirectmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Reversible transformation from amorphouse Na3Fe3(SO4)2(OH)6 to crystallized NaFe3(SO4)2(OH)6 Jarosite-type hydroxysulfate

et al. 2015

Self Cite

View full text Add to dashboard Cite

“…Note therefore that such structural reversibility from crystallized to amorphous phase was already reported in an iron sulfate based material. 36 In order to better get insight the structural transformation we focus our study in the potential window 4-1. Figure 3a).…”

Section: Resultsmentioning

confidence: 99%

Reversible Li Insertion Studies on V₄O₃(PO₄)₃as High Energy Storage Material for Li-Ion Battery Applications

Satyanarayana¹,

Rao²,

Pralong³

et al. 2016

J. Electrochem. Soc.

Self Cite

View full text Add to dashboard Cite

Li-insertion studies were performed on V 4 O 3 (PO 4 ) 3 that belongs to the libscombite/lazulite family. Availability of multiple oxidation states and vacancies in crystal structure allows for the insertion of more than 7 lithium ions per formula unit. We will show that in the voltage window of 1-4 V vs. Li + /Li, 6.0 Li-ions could be inserted leading to a reversible capacity of 195 mAh/g at a C/5 rate. A structural transformation is observed from ex-situ XRD patterns after the insertion of 2 lithium at 2.4 V vs. Li + /Li, consistent with the available crystallographic sites in the structure. Interestingly we show that from this phase Li 2 V 4 O 3 (PO 4 ) 3 , further lithium insertion lead to an amorphous material but the structure is completely recovered on charge. Layered hexagonal transition metal oxides LiMO 2 (here, M = Co, Mn, Ni, Fe, Cr) have been extensively studied for commercial Li-ion secondary battery applications.1,2 The substitution of Ni and Mn in LiCoO 2 results in composition of LiNi 1/3 Mn 1/3 Co 1/3 O 2 is proven to be a promising cathode material.3-6 Spinel LiMn 2 O 4 has shown more interest due to less toxic nature of Mn, but lagged in the competition for next generation cheap energy storage device in presence of manganese dissolution in electrolyte and structural instability. 7,8 To make structurally and electrochemically stable spinel LiMn 2 O 4 , the manganese (Mn) ion substituted with Ti, Cr, Fe, Co, Ni, Al and Mg were explored. 7,9-13 Even though layered and spinel transition metal oxides are extensively studied for Li ion battery applications, there is an existence of crystal structural problems while on charging to higher voltage where the electrolyte is unstable due to evolution of oxygen from de-lithiated transition metal oxide framework. To address this problem, more research focus on lithium containing metal phosphate LiFePO 4 , LiMnPO 4 , Li 3 V 2 (PO 4 ) 3 etc.14-16 have been explored as thermally stable electrode materials. Indeed, the bonding of oxygen to phosphorous stabilize the structure from oxygen evolution, differently to layered transition metal oxides whereas oxygen evolution occurs at high charge voltages.17,18 But the energy obtained for these materials is low compared to metal oxide materials due to its high molecular weight. To compensate the energy density of metal polyanionic materials, the number of electrons transferred per unit formula has to increase through oxidation or reduction of transition metal ions vs. ExperimentalFor the synthesis route of V 4 O 3 (PO 4 ) 3 , we use the same route that was described by E. Benser and co-workers 32 in which stoichiometric amounts of homemade precursors VO 2 , VPO 4 , and (VO) 2 P 2 O 7 are placed in a carbon coated evacuated quart tube at 800• C for the period of five days.The X-ray diffraction pattern was recorded in the 2θ scale range of 10-120• , Cu Kα as X-ray source using BRUKER (D8) diffractometer and Co Kα as X-ray source using PAN analytical diffractometer. Rietveld refinement was carried out using FULLPROF so...

show abstract

Polyanionic Insertion Materials for Sodium‐Ion Batteries

Barpanda

Lander

Nishimura

et al. 2018

Advanced Energy Materials

340

185

View full text Add to dashboard Cite

future. [1][2][3] To avoid this scenario, Na-ion batteries can play a vital role. Contrary to Li, Na has abundant natural resources with even geographic distribution. In addition to being the fifth-most abundant element in earth's crust, the Na charge carrier is also the second lightest alkali element in the periodic table. In this context, mammoth effort has been geared to build efficient Na-ion batteries. 2D layered oxides are the most important category of cathode materials, which has been proven by their dominance in commercial Li-ion batteries. Although the only difference is the intercalation ion, the electrochemical behavior and structure transformation of Na analogs are very different to that in Li-ion batteries. These are mainly caused by the larger size of Na, which can stabilize the layered structure (empirical stability criterion for ABO 2 : r B /r A <0.86 for α-NaFeO 2 type structure) and thus prevent Na from occupying tetrahedral sites and promote Na cation ordering. [31] NaMO 2 compounds can retain the layered structure for all 3d transition elements M, whereas Co and Ni are the exclusive 3d transition metals that can offer ground state stability of layered structure of LiMO 2 . Thereby, intensive survey for a variety of NaMO 2 compounds was performed. [4][5][6]32] However, even with the inherently stable structural nature of NaMO 2 compounds, they usually suffer from a slopy voltage profile distributed over a wide potential range at lower average voltage (at least 0.3 V and in many cases over 0.5 V) as compared to the Li analog, identifying only a few complicated compounds that can generate >3.5 V versus Na/Na + .Development of high voltage cathode materials is of paramount importance for Na batteries, bearing in mind the relative difference in anode potential of Li/Li + : −3.03 V and Na/ Na + : −2.71 V versus NHE. With an essential lack of high-voltage layered cathode material, polyanion compounds form a major stream toward the stable cathode materials operating over 3.5 V in Na batteries. Light and small polyanion units such as (SO 4 ) 2− , (PO 4 ) 3− , (BO 3 ) 3− , (SiO 4 ) 4− , which have also been widely explored as major components in Li-ion battery cathodes, offer two major functions; i) raising the redox potential largely as compared to the simple oxides with identical redox couple, and ii) providing inherent safety to the battery system. These two very important features led olivine LiFePO 4 to a great commercial success in the Li battery market over a decade ago, [35,37,38,63] proving that additional atoms X (X = P in this case), other than Efficient energy storage is a driving factor propelling myriads of mobile electronics, electric vehicles and stationary electric grid storage. Li-ion batteries have realized these goals in a commercially viable manner with ever increasing penetration to different technology sectors across the globe. While these electronic devices are more evident and appealing to consumers, there has been a growing concern for micro-to-mega grid storage systems. Ove...

show abstract

Lithium Intercalation into the Jarosite-type Hydroxysulfate: A Topotactic Reversible Reaction from a Crystalline Phase to an Inorganic Polymer-like Structure

Cited by 31 publications

References 18 publications

Reversible transformation from amorphouse Na3Fe3(SO4)2(OH)6 to crystallized NaFe3(SO4)2(OH)6 Jarosite-type hydroxysulfate

Reversible transformation from amorphouse Na3Fe3(SO4)2(OH)6 to crystallized NaFe3(SO4)2(OH)6 Jarosite-type hydroxysulfate

Reversible Li Insertion Studies on V₄O₃(PO₄)₃as High Energy Storage Material for Li-Ion Battery Applications

Polyanionic Insertion Materials for Sodium‐Ion Batteries

Contact Info

Product

Resources

About

Lithium Intercalation into the Jarosite-type Hydroxysulfate: A Topotactic Reversible Reaction from a Crystalline Phase to an Inorganic Polymer-like Structure

Cited by 31 publications

References 18 publications

Reversible transformation from amorphouse Na3Fe3(SO4)2(OH)6 to crystallized NaFe3(SO4)2(OH)6 Jarosite-type hydroxysulfate

Reversible transformation from amorphouse Na3Fe3(SO4)2(OH)6 to crystallized NaFe3(SO4)2(OH)6 Jarosite-type hydroxysulfate

Reversible Li Insertion Studies on V4O3(PO4)3as High Energy Storage Material for Li-Ion Battery Applications

Polyanionic Insertion Materials for Sodium‐Ion Batteries

Contact Info

Product

Resources

About

Reversible Li Insertion Studies on V₄O₃(PO₄)₃as High Energy Storage Material for Li-Ion Battery Applications